JPH04318071A - Coating compound composition and coated aluminum material - Google Patents
Coating compound composition and coated aluminum materialInfo
- Publication number
- JPH04318071A JPH04318071A JP8513691A JP8513691A JPH04318071A JP H04318071 A JPH04318071 A JP H04318071A JP 8513691 A JP8513691 A JP 8513691A JP 8513691 A JP8513691 A JP 8513691A JP H04318071 A JPH04318071 A JP H04318071A
- Authority
- JP
- Japan
- Prior art keywords
- water
- soluble
- film
- coating
- pts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 17
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 15
- 238000000576 coating method Methods 0.000 title abstract description 28
- 239000011248 coating agent Substances 0.000 title abstract description 26
- 239000000203 mixture Substances 0.000 title abstract description 26
- 150000001875 compounds Chemical class 0.000 title abstract description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 230000007797 corrosion Effects 0.000 claims abstract description 36
- 238000005260 corrosion Methods 0.000 claims abstract description 36
- 229920005989 resin Polymers 0.000 claims abstract description 28
- 239000011347 resin Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000314 lubricant Substances 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 21
- 239000003112 inhibitor Substances 0.000 claims abstract description 15
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 15
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 13
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 12
- 239000008199 coating composition Substances 0.000 claims description 23
- 239000007787 solid Substances 0.000 abstract description 26
- 239000002245 particle Substances 0.000 abstract description 18
- 238000012545 processing Methods 0.000 abstract description 13
- UOFGSWVZMUXXIY-UHFFFAOYSA-N 1,5-Diphenyl-3-thiocarbazone Chemical compound C=1C=CC=CC=1N=NC(=S)NNC1=CC=CC=C1 UOFGSWVZMUXXIY-UHFFFAOYSA-N 0.000 abstract description 2
- -1 hydrogen ions Chemical class 0.000 description 24
- 238000000034 method Methods 0.000 description 18
- 239000003973 paint Substances 0.000 description 18
- 229920000178 Acrylic resin Polymers 0.000 description 17
- 239000004925 Acrylic resin Substances 0.000 description 17
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 15
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000000126 substance Substances 0.000 description 10
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 8
- 239000002253 acid Substances 0.000 description 8
- 239000004094 surface-active agent Substances 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000003921 oil Substances 0.000 description 6
- 235000019353 potassium silicate Nutrition 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 6
- 239000001993 wax Substances 0.000 description 6
- HYZJCKYKOHLVJF-UHFFFAOYSA-N 1H-benzimidazole Chemical compound C1=CC=C2NC=NC2=C1 HYZJCKYKOHLVJF-UHFFFAOYSA-N 0.000 description 5
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 5
- WZUUZPAYWFIBDF-UHFFFAOYSA-N 5-amino-1,2-dihydro-1,2,4-triazole-3-thione Chemical compound NC1=NNC(S)=N1 WZUUZPAYWFIBDF-UHFFFAOYSA-N 0.000 description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 229910002012 Aerosil® Inorganic materials 0.000 description 4
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 4
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 4
- JOZYBUSXAGFNKN-UHFFFAOYSA-N N-pyridin-2-ylpyridin-2-amine Chemical compound N(c1ccccn1)c1ccccn1.N(c1ccccn1)c1ccccn1 JOZYBUSXAGFNKN-UHFFFAOYSA-N 0.000 description 4
- 229920001214 Polysorbate 60 Polymers 0.000 description 4
- 229920003180 amino resin Polymers 0.000 description 4
- 229910021529 ammonia Inorganic materials 0.000 description 4
- 239000008119 colloidal silica Substances 0.000 description 4
- 125000004122 cyclic group Chemical group 0.000 description 4
- 235000014113 dietary fatty acids Nutrition 0.000 description 4
- 239000000194 fatty acid Substances 0.000 description 4
- 229930195729 fatty acid Natural products 0.000 description 4
- 239000000178 monomer Substances 0.000 description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 230000006378 damage Effects 0.000 description 3
- 238000005238 degreasing Methods 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000010419 fine particle Substances 0.000 description 3
- 229910021485 fumed silica Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000000344 soap Substances 0.000 description 3
- YXIWHUQXZSMYRE-UHFFFAOYSA-N 1,3-benzothiazole-2-thiol Chemical compound C1=CC=C2SC(S)=NC2=C1 YXIWHUQXZSMYRE-UHFFFAOYSA-N 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 2
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- NWGKJDSIEKMTRX-AAZCQSIUSA-N Sorbitan monooleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O NWGKJDSIEKMTRX-AAZCQSIUSA-N 0.000 description 2
- IYFATESGLOUGBX-YVNJGZBMSA-N Sorbitan monopalmitate Chemical compound CCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O IYFATESGLOUGBX-YVNJGZBMSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 2
- LWZFANDGMFTDAV-BURFUSLBSA-N [(2r)-2-[(2r,3r,4s)-3,4-dihydroxyoxolan-2-yl]-2-hydroxyethyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O LWZFANDGMFTDAV-BURFUSLBSA-N 0.000 description 2
- 229920000180 alkyd Polymers 0.000 description 2
- 150000005215 alkyl ethers Chemical class 0.000 description 2
- CEGOLXSVJUTHNZ-UHFFFAOYSA-K aluminium tristearate Chemical compound [Al+3].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CEGOLXSVJUTHNZ-UHFFFAOYSA-K 0.000 description 2
- 229940063655 aluminum stearate Drugs 0.000 description 2
- 125000000129 anionic group Chemical group 0.000 description 2
- IOJUPLGTWVMSFF-UHFFFAOYSA-N benzothiazole Chemical compound C1=CC=C2SC=NC2=C1 IOJUPLGTWVMSFF-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003093 cationic surfactant Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 2
- 238000007602 hot air drying Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920001568 phenolic resin Polymers 0.000 description 2
- 239000005011 phenolic resin Substances 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- ZSKGQVFRTSEPJT-UHFFFAOYSA-N pyrrole-2-carboxaldehyde Chemical compound O=CC1=CC=CN1 ZSKGQVFRTSEPJT-UHFFFAOYSA-N 0.000 description 2
- 238000007788 roughening Methods 0.000 description 2
- 125000005372 silanol group Chemical group 0.000 description 2
- 229950006451 sorbitan laurate Drugs 0.000 description 2
- 235000011067 sorbitan monolaureate Nutrition 0.000 description 2
- 229950004959 sorbitan oleate Drugs 0.000 description 2
- 229950003429 sorbitan palmitate Drugs 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- JNYAEWCLZODPBN-JGWLITMVSA-N (2r,3r,4s)-2-[(1r)-1,2-dihydroxyethyl]oxolane-3,4-diol Chemical class OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O JNYAEWCLZODPBN-JGWLITMVSA-N 0.000 description 1
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 1
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 description 1
- FMCUPJKTGNBGEC-UHFFFAOYSA-N 1,2,4-triazol-4-amine Chemical compound NN1C=NN=C1 FMCUPJKTGNBGEC-UHFFFAOYSA-N 0.000 description 1
- BNSNUHPJRKTRNT-UHFFFAOYSA-N 1,3-dianilinothiourea Chemical compound C=1C=CC=CC=1NNC(=S)NNC1=CC=CC=C1 BNSNUHPJRKTRNT-UHFFFAOYSA-N 0.000 description 1
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 description 1
- RAIPHJJURHTUIC-UHFFFAOYSA-N 1,3-thiazol-2-amine Chemical compound NC1=NC=CS1 RAIPHJJURHTUIC-UHFFFAOYSA-N 0.000 description 1
- WGJCBBASTRWVJL-UHFFFAOYSA-N 1,3-thiazolidine-2-thione Chemical compound SC1=NCCS1 WGJCBBASTRWVJL-UHFFFAOYSA-N 0.000 description 1
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 description 1
- VGIVYSWGHVFQRP-UHFFFAOYSA-N 1-anilino-3-phenylthiourea Chemical compound C=1C=CC=CC=1NC(=S)NNC1=CC=CC=C1 VGIVYSWGHVFQRP-UHFFFAOYSA-N 0.000 description 1
- YTQQIHUQLOZOJI-UHFFFAOYSA-N 2,3-dihydro-1,2-thiazole Chemical compound C1NSC=C1 YTQQIHUQLOZOJI-UHFFFAOYSA-N 0.000 description 1
- FLFWJIBUZQARMD-UHFFFAOYSA-N 2-mercapto-1,3-benzoxazole Chemical compound C1=CC=C2OC(S)=NC2=C1 FLFWJIBUZQARMD-UHFFFAOYSA-N 0.000 description 1
- SDXAWLJRERMRKF-UHFFFAOYSA-N 3,5-dimethyl-1h-pyrazole Chemical compound CC=1C=C(C)NN=1 SDXAWLJRERMRKF-UHFFFAOYSA-N 0.000 description 1
- ZDZYGYFHTPFREM-UHFFFAOYSA-N 3-[3-aminopropyl(dimethoxy)silyl]oxypropan-1-amine Chemical compound NCCC[Si](OC)(OC)OCCCN ZDZYGYFHTPFREM-UHFFFAOYSA-N 0.000 description 1
- ZYAASQNKCWTPKI-UHFFFAOYSA-N 3-[dimethoxy(methyl)silyl]propan-1-amine Chemical compound CO[Si](C)(OC)CCCN ZYAASQNKCWTPKI-UHFFFAOYSA-N 0.000 description 1
- VVEQSNONASWWMH-UHFFFAOYSA-N 3h-1,3-benzoselenazole-2-thione Chemical compound C1=CC=C2[se]C(S)=NC2=C1 VVEQSNONASWWMH-UHFFFAOYSA-N 0.000 description 1
- YIROYDNZEPTFOL-UHFFFAOYSA-N 5,5-Dimethylhydantoin Chemical compound CC1(C)NC(=O)NC1=O YIROYDNZEPTFOL-UHFFFAOYSA-N 0.000 description 1
- GDGIVSREGUOIJZ-UHFFFAOYSA-N 5-amino-3h-1,3,4-thiadiazole-2-thione Chemical compound NC1=NN=C(S)S1 GDGIVSREGUOIJZ-UHFFFAOYSA-N 0.000 description 1
- GZVHEAJQGPRDLQ-UHFFFAOYSA-N 6-phenyl-1,3,5-triazine-2,4-diamine Chemical compound NC1=NC(N)=NC(C=2C=CC=CC=2)=N1 GZVHEAJQGPRDLQ-UHFFFAOYSA-N 0.000 description 1
- 229910002014 Aerosil® 130 Inorganic materials 0.000 description 1
- 229910002018 Aerosil® 300 Inorganic materials 0.000 description 1
- 229910002019 Aerosil® 380 Inorganic materials 0.000 description 1
- 229910000838 Al alloy Inorganic materials 0.000 description 1
- KLSJWNVTNUYHDU-UHFFFAOYSA-N Amitrole Chemical compound NC1=NC=NN1 KLSJWNVTNUYHDU-UHFFFAOYSA-N 0.000 description 1
- 229910052582 BN Inorganic materials 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229920000298 Cellophane Polymers 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- BWLUMTFWVZZZND-UHFFFAOYSA-N Dibenzylamine Chemical compound C=1C=CC=CC=1CNCC1=CC=CC=C1 BWLUMTFWVZZZND-UHFFFAOYSA-N 0.000 description 1
- KSPIHGBHKVISFI-UHFFFAOYSA-N Diphenylcarbazide Chemical compound C=1C=CC=CC=1NNC(=O)NNC1=CC=CC=C1 KSPIHGBHKVISFI-UHFFFAOYSA-N 0.000 description 1
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920006197 POE laurate Polymers 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- HVUMOYIDDBPOLL-XWVZOOPGSA-N Sorbitan monostearate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OC[C@@H](O)[C@H]1OC[C@H](O)[C@H]1O HVUMOYIDDBPOLL-XWVZOOPGSA-N 0.000 description 1
- LJTFFORYSFGNCT-UHFFFAOYSA-N Thiocarbohydrazide Chemical compound NNC(=S)NN LJTFFORYSFGNCT-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- IBVAQQYNSHJXBV-UHFFFAOYSA-N adipic acid dihydrazide Chemical compound NNC(=O)CCCCC(=O)NN IBVAQQYNSHJXBV-UHFFFAOYSA-N 0.000 description 1
- 150000003973 alkyl amines Chemical class 0.000 description 1
- 125000005907 alkyl ester group Chemical group 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 239000002280 amphoteric surfactant Substances 0.000 description 1
- 239000003945 anionic surfactant Substances 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- XEVRDFDBXJMZFG-UHFFFAOYSA-N carbonyl dihydrazine Chemical compound NNC(=O)NN XEVRDFDBXJMZFG-UHFFFAOYSA-N 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- BHDFTVNXJDZMQK-UHFFFAOYSA-N chloromethane;2-(dimethylamino)ethyl 2-methylprop-2-enoate Chemical compound ClC.CN(C)CCOC(=O)C(C)=C BHDFTVNXJDZMQK-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- AFZSMODLJJCVPP-UHFFFAOYSA-N dibenzothiazol-2-yl disulfide Chemical compound C1=CC=C2SC(SSC=3SC4=CC=CC=C4N=3)=NC2=C1 AFZSMODLJJCVPP-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000001804 emulsifying effect Effects 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 150000002193 fatty amides Chemical class 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- LNEPOXFFQSENCJ-UHFFFAOYSA-N haloperidol Chemical compound C1CC(O)(C=2C=CC(Cl)=CC=2)CCN1CCCC(=O)C1=CC=C(F)C=C1 LNEPOXFFQSENCJ-UHFFFAOYSA-N 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 229920001903 high density polyethylene Polymers 0.000 description 1
- 239000004700 high-density polyethylene Substances 0.000 description 1
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000005660 hydrophilic surface Effects 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000001023 inorganic pigment Substances 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QLOAVXSYZAJECW-UHFFFAOYSA-N methane;molecular fluorine Chemical compound C.FF QLOAVXSYZAJECW-UHFFFAOYSA-N 0.000 description 1
- PMRYVIKBURPHAH-UHFFFAOYSA-N methimazole Chemical compound CN1C=CNC1=S PMRYVIKBURPHAH-UHFFFAOYSA-N 0.000 description 1
- KQSSATDQUYCRGS-UHFFFAOYSA-N methyl glycinate Chemical compound COC(=O)CN KQSSATDQUYCRGS-UHFFFAOYSA-N 0.000 description 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 1
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 1
- 239000012170 montan wax Substances 0.000 description 1
- NOUUUQMKVOUUNR-UHFFFAOYSA-N n,n'-diphenylethane-1,2-diamine Chemical compound C=1C=CC=CC=1NCCNC1=CC=CC=C1 NOUUUQMKVOUUNR-UHFFFAOYSA-N 0.000 description 1
- KBJFYLLAMSZSOG-UHFFFAOYSA-N n-(3-trimethoxysilylpropyl)aniline Chemical compound CO[Si](OC)(OC)CCCNC1=CC=CC=C1 KBJFYLLAMSZSOG-UHFFFAOYSA-N 0.000 description 1
- BOQKCADLPNLYCZ-UHFFFAOYSA-N n-phenylbenzenecarbothioamide Chemical compound C=1C=CC=CC=1C(=S)NC1=CC=CC=C1 BOQKCADLPNLYCZ-UHFFFAOYSA-N 0.000 description 1
- MWCGLTCRJJFXKR-UHFFFAOYSA-N n-phenylethanethioamide Chemical compound CC(=S)NC1=CC=CC=C1 MWCGLTCRJJFXKR-UHFFFAOYSA-N 0.000 description 1
- 229920002114 octoxynol-9 Polymers 0.000 description 1
- ZQPPMHVWECSIRJ-KTKRTIGZSA-M oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC([O-])=O ZQPPMHVWECSIRJ-KTKRTIGZSA-M 0.000 description 1
- 229940049964 oleate Drugs 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012860 organic pigment Substances 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920001225 polyester resin Polymers 0.000 description 1
- 239000004645 polyester resin Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920000259 polyoxyethylene lauryl ether Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 229940100515 sorbitan Drugs 0.000 description 1
- 229950011392 sorbitan stearate Drugs 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- ITRNXVSDJBHYNJ-UHFFFAOYSA-N tungsten disulfide Chemical compound S=[W]=S ITRNXVSDJBHYNJ-UHFFFAOYSA-N 0.000 description 1
- 238000009423 ventilation Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- XOOUIPVCVHRTMJ-UHFFFAOYSA-L zinc stearate Chemical compound [Zn+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O XOOUIPVCVHRTMJ-UHFFFAOYSA-L 0.000 description 1
Landscapes
- Paints Or Removers (AREA)
Abstract
Description
【0001】0001
【産業上の利用分野】本発明は、塗料組成物及び該組成
物から得られた親水性皮膜を有する被覆アルミニウム材
に関する。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a coating composition and a coated aluminum material having a hydrophilic film obtained from the composition.
【0002】0002
【従来の技術】近年、耐食性等の本来の性能を全く損う
ことなく、しかも表面が親水性を有するような塗膜を得
るための塗料組成物に対する要望が強くなってきている
。例えば、ルームエアコンの急激な普及に伴って、熱交
換器用のフィン材の需要が大幅に伸びているが、このよ
うなフィン材に対して前記のような特殊な性能を有する
塗料が要求されているのである。BACKGROUND OF THE INVENTION In recent years, there has been an increasing demand for a coating composition that can provide a coating film with a hydrophilic surface without impairing its original properties such as corrosion resistance. For example, with the rapid spread of room air conditioners, the demand for fin materials for heat exchangers has increased significantly, but paints with the special performance mentioned above are required for such fin materials. There is.
【0003】前記フィン材としては軽量化、加工性及び
熱伝導性の観点からアルミニウム及び/又はアルミニウ
ム合金(以下、本発明では単に「アルミニウム」という
)が広く使用されている。該フィン材は熱交換率の向上
、即ち表面の水濡れ性を良くする目的で、アルミニウム
表面にベーマイト処理等の化成処理を施すか、塗装処理
が行われるのが一般的である。これは、アルミニウムの
防食とともに、熱交換器の運転中に発生する凝縮水の付
着による通風抵抗の増大を防止し、熱交換効率の向上を
計るためである。[0003] As the fin material, aluminum and/or aluminum alloys (hereinafter simply referred to as "aluminum" in the present invention) are widely used from the viewpoints of weight reduction, workability, and thermal conductivity. The fin material is generally subjected to a chemical conversion treatment such as boehmite treatment or a coating treatment to the aluminum surface in order to improve the heat exchange efficiency, that is, to improve the water wettability of the surface. This is to prevent corrosion of aluminum, prevent increase in ventilation resistance due to adhesion of condensed water generated during operation of the heat exchanger, and improve heat exchange efficiency.
【0004】塗料を塗装することによって前記性能を有
する皮膜を形成させる方法としては、大別して無機質(
主として水ガラス)皮膜を形成させる方法と、有機質皮
膜を形成させる方法が知られている。無機質(水ガラス
)皮膜を形成させる方法としては、例えば特開昭58−
126989号公報や特公昭55−1347 号公報に
記載の方法が知られている。しかし、この方法により形
成された水ガラス皮膜は、凝縮水により徐々に溶解する
ため、皮膜表面の親水性の持続性及び耐食性に問題があ
った。[0004] Methods for forming a film having the above performance by applying a paint can be roughly divided into inorganic (
A method of forming a film (mainly water glass) and a method of forming an organic film are known. As a method for forming an inorganic (water glass) film, for example, JP-A-58-
Methods described in Japanese Patent Publication No. 126989 and Japanese Patent Publication No. 55-1347 are known. However, since the water glass film formed by this method is gradually dissolved by condensed water, there have been problems with the durability of hydrophilicity and corrosion resistance of the film surface.
【0005】また、クロメート系処理により耐食性皮膜
を形成させた後、無機質(水ガラス)皮膜を形成させる
方法(特開昭59−13078号公報、特開昭50−3
8645号公報)も知られており、これらの方法によっ
ても、耐食性は向上するが、水ガラスの溶解による親水
持続性の低下という基本的な問題点は解決していなかっ
た。その上これらの方法はクロメート系処理によるクロ
ム等の重金属を含む排水処理が必要であり、更に塗布工
程が2回になるため、1回塗りに比べて処理設備が大き
くなる等、工程数や設備の点で割高になるという問題点
もあった。[0005] There is also a method of forming an inorganic (water glass) film after forming a corrosion-resistant film by chromate treatment (Japanese Patent Application Laid-Open Nos. 59-13078 and 1983-3).
No. 8645) is also known, and although these methods improve corrosion resistance, they do not solve the fundamental problem of reduced hydrophilicity due to dissolution of water glass. Furthermore, these methods require treatment of wastewater containing heavy metals such as chromium using chromate treatment, and since the application process is performed twice, the processing equipment is larger than that required for one-time application. There was also the problem that it was relatively expensive.
【0006】一方、有機質皮膜を形成させる方法として
は、有機樹脂と有機微粒子あるいは吸水性有機微粒子、
及び界面活性剤から成る塗料を塗布する方法がある(特
開昭62−129366 号公報、特開昭63−372
号公報)。しかし、最近は熱交換器の小型化、軽量化の
ためフィン材の間隔が狭くなっており、そのため高度の
親水性が要求されてきているが、前記有機微粒子あるい
は吸水性樹脂粒子では、要求される親水性が発揮できな
かった。On the other hand, as a method for forming an organic film, organic resin and organic fine particles or water-absorbing organic fine particles,
There is a method of applying a paint consisting of surfactants and surfactants (JP-A-62-129366, JP-A-63-372).
Publication No.). However, in recent years, the spacing between fin materials has become narrower in order to make heat exchangers smaller and lighter, which has required a high degree of hydrophilicity. The hydrophilic properties could not be exhibited.
【0007】その他、有機樹脂に水ガラス、シリカ、水
酸化アルミニウム、炭酸カルシウム、チタニア等を混合
し、必要により界面活性剤を併用した塗料(特開昭61
−225044 号公報)や、有機−無機(シリカ)複
合体と界面活性剤よりなる塗料(特開昭59−1701
70 号公報)を塗布する方法も知られているが、いず
れも皮膜の耐食性の点で不充分であった。[0007] In addition, there is a paint (Japanese Unexamined Patent Application Publication No. 1983-1992) in which organic resin is mixed with water glass, silica, aluminum hydroxide, calcium carbonate, titania, etc., and if necessary, a surfactant is used.
-225044) and paints made of organic-inorganic (silica) composites and surfactants (JP-A-59-1701).
70) is also known, but both methods were insufficient in terms of the corrosion resistance of the film.
【0008】又、最近では工程の簡略化、塗膜の均一性
などの観点から、成形前のアルミニウムコイルに塗装し
、塗膜形成後これを所定の形状に成形加工するプレコー
ト法に対する期待が高まって来ている。前記成形加工に
おいても、従来のドロー加工法(張出、絞り加工)から
、より条件の厳しいドローレス加工法(しごき加工)に
変って来ており、前述の如き従来の塗料組成物は、金型
の摩耗、成形不良、あるいは親水性塗膜の損傷等の問題
点があった。[0008] Recently, from the viewpoint of process simplification and uniformity of the coating film, expectations have been increasing for the pre-coating method, in which the aluminum coil is coated before forming, and after the coating film is formed, it is formed into a predetermined shape. It's coming. In the above-mentioned molding process, there has been a change from the conventional draw processing method (stretching, drawing processing) to the drawless processing method (ironing processing), which requires stricter conditions. There were problems such as wear, poor molding, and damage to the hydrophilic coating.
【0009】更に、プレス加工時には加工油を塗布して
成形加工し、加工後トリクロルエチレン等により脱脂洗
浄して加工油を除去するのが一般的であるが、最近トリ
クロロエチレンやフロン等はオゾン層の破壊や水質汚濁
等の地球環境破壊の観点からその使用が規制されるよう
になって来ている。従って、プレス加工時には脱脂洗浄
が不要な加工油(洗浄レスタイプの加工油)が使用され
て来ている。前記洗浄レスタイプの加工油は揮発性であ
り、従来の洗浄工程の代りに熱風乾燥工程を用いて脱脂
される。Furthermore, during press processing, it is common practice to apply processing oil and perform the forming process, and after processing, remove the processing oil by degreasing and cleaning with trichlorethylene, etc., but recently, trichlorethylene, fluorocarbons, etc. Their use has come to be regulated from the viewpoint of destruction of the global environment such as destruction and water pollution. Therefore, processing oils that do not require degreasing and cleaning (cleaning-less type processing oils) have been used during press processing. The cleaning-less type processing oil is volatile and is degreased using a hot air drying process instead of the conventional cleaning process.
【0010】熱風乾燥による脱脂は有機溶剤によるそれ
よりも脱脂能力が劣るため、特に表面の親水性を要求さ
れるような部材においては、残留加工油の影響を押える
ために初期塗膜の親水性をより高度にする必要があった
。しかし、従来の塗料組成物では、要求される程度の親
水性がなかなか得られないのが現状であった。Since the degreasing ability of hot air drying is inferior to that of organic solvents, it is necessary to increase the hydrophilicity of the initial coating film in order to suppress the influence of residual processing oil, especially for parts that require surface hydrophilicity. needed to be more advanced. However, with conventional coating compositions, it has been difficult to obtain the required level of hydrophilicity.
【0011】[0011]
【発明が解決しようとする課題】本発明は、前記従来技
術の問題点を解決し、塗料の安定性、皮膜の密着性、プ
レス加工性、親水性、親水持続性、及び耐食性に優れた
塗料組成物並びに該塗料組成物を塗布したアルミニウム
材を提供することを目的とする。[Problems to be Solved by the Invention] The present invention solves the problems of the prior art and provides a paint that has excellent paint stability, film adhesion, press workability, hydrophilicity, hydrophilic sustainability, and corrosion resistance. The object of the present invention is to provide a composition and an aluminum material coated with the coating composition.
【0012】0012
【課題を解決するための手段】即ち、本発明は、(1)
(a)水溶性又は水分散性有機樹脂、(b)分子中に窒
素原子を有する有機腐食抑制剤、(c)シリカ粒子、(
d)潤滑剤粉末、(e)ノニオン系界面活性剤、及び(
f)水
から成る塗料組成物、及び
(2)(a)水溶性又は水分散性有機樹脂、(b)分子
中に窒素原子を有する有機腐食抑制剤、(c)シリカ粒
子、(d)潤滑剤粉末、及び(e)ノニオン系界面活性
剤
から成る親水性皮膜を有する被覆アルミニウム材に関す
る。[Means for Solving the Problems] That is, the present invention provides (1)
(a) water-soluble or water-dispersible organic resin, (b) organic corrosion inhibitor having nitrogen atoms in the molecule, (c) silica particles, (
d) lubricant powder, (e) nonionic surfactant, and (
f) a coating composition consisting of water, and (2) (a) a water-soluble or water-dispersible organic resin, (b) an organic corrosion inhibitor having a nitrogen atom in its molecule, (c) silica particles, and (d) a lubricant. and (e) a nonionic surfactant.
【0013】本発明の塗料組成物に使用される(a)水
溶性または水分散性樹脂としては、例えば水溶性もしく
は水分散性のアクリル系樹脂、ポリエステル系樹脂、エ
ポキシ系樹脂、アルキド系樹脂、アクリルアルキド系樹
脂、ポリビニルアルコール系樹脂等が挙げられる。これ
らの樹脂は一般に市販されているものが使用可能であり
、またこれらは一種もしくは二種以上を混合して使用し
てもよい。Examples of the water-soluble or water-dispersible resin (a) used in the coating composition of the present invention include water-soluble or water-dispersible acrylic resins, polyester resins, epoxy resins, alkyd resins, Examples include acrylic alkyd resins and polyvinyl alcohol resins. Generally commercially available resins can be used, and these resins may be used alone or in combination of two or more.
【0014】尚、本発明においては、皮膜の親水性及び
耐食性の観点から、前記樹脂は水酸基価が20〜420
mg KOH/g(対固形分)、及び/または酸価が1
0〜300mg KOH/g(対固形分)の範囲にある
ことが特に好ましい。前記範囲よりも水酸基価及び/ま
たは酸価の値が小さい場合には、皮膜の親水性が不充分
になる可能性があり、一方値が大きい場合には塗膜の耐
食性、耐水性が低下する傾向になる。In the present invention, from the viewpoint of hydrophilicity and corrosion resistance of the film, the resin has a hydroxyl value of 20 to 420.
mg KOH/g (based on solid content) and/or acid value of 1
A range of 0 to 300 mg KOH/g (based on solid content) is particularly preferred. If the hydroxyl value and/or acid value is smaller than the above range, the hydrophilicity of the coating may become insufficient, while if the value is large, the corrosion resistance and water resistance of the coating will decrease. become a trend.
【0015】また本発明塗料組成物に使用される(b)
分子中に窒素原子を有する有機腐食抑制剤は、塗布され
た場合に基材に対して配向する性質を有しているので、
基材表面に均一のバリヤー層を形成するため、耐食性向
上に大きく寄与するのである。さらに前記有機腐食抑制
剤は、本発明塗料組成物中の他の成分である水溶性もし
くは水分散性有機樹脂や、シリカ粒子と焼付硬化時には
反応することが認められ、従って形成された皮膜と基材
との密着性や、シリカ粒子の固定化にも寄与するもので
ある。(b) also used in the coating composition of the present invention
Organic corrosion inhibitors that have nitrogen atoms in their molecules have the property of being oriented toward the base material when applied.
Since it forms a uniform barrier layer on the surface of the base material, it greatly contributes to improving corrosion resistance. Furthermore, it has been observed that the organic corrosion inhibitor reacts with water-soluble or water-dispersible organic resins and silica particles, which are other components in the coating composition of the present invention, during baking hardening, and therefore, the formed film and base It also contributes to adhesion to materials and immobilization of silica particles.
【0016】本発明において、有機腐食抑制剤とは、塗
料中に少量添加されて、その塗料を塗布して金属の腐食
を抑制する「分子中に窒素原子を有する有機系の化合物
」を示す。前記腐食抑制剤は、窒素原子のもつ非共有電
子対に塗料中の水素イオンが配位してアンモニウムイオ
ンとなり、これが正電荷をもつ親水基として金属のカソ
ードへ吸着するとともに、金属原子と窒素原子との電気
陰性度の差により、窒素原子のもつ非共有電子対が直接
金属自体と配位共有結合することにより、金属の分極や
極間抵抗を増大させ、金属の腐食を抑制するものである
。[0016] In the present invention, the term "organic corrosion inhibitor" refers to an "organic compound having a nitrogen atom in its molecule" which is added in a small amount to a paint to suppress corrosion of metals when the paint is applied. In the corrosion inhibitor, hydrogen ions in the paint coordinate with the lone pair of electrons of the nitrogen atom to form ammonium ions, which are adsorbed to the metal cathode as positively charged hydrophilic groups, and the metal atoms and nitrogen atoms Due to the difference in electronegativity, the nitrogen atom's lone pair of electrons forms a direct covalent bond with the metal itself, increasing the metal's polarization and interelectrode resistance, and suppressing metal corrosion. .
【0017】前記(b)分子中に窒素原子を有する有機
腐食抑制剤の具体例としては、例えば
(i) 5員環、6員環等の環状構造を有し、環状構造
中に窒素原子を有さない化合物:例えばジフェニルチオ
カルバゾン、N,N′−ジフェニルエチレンジアミン、
S−ジフェニルカルバジド、ジベンジルアミン、1,5
−ジフェニル−3−チオカルボヒドラジド、1,4−ジ
フェニル−3−チオセミカルバジド、チオカルボアニラ
イド、チオベンズアニライド、チオアセトアニライド等
、(ii)5員環、6員環等の環状構造を有し、環状構
造中に窒素原子を有する化合物:例えば2−メルカプト
ベンゾチアゾール、ベンゾトリアゾール、1−ヒドロキ
シ−ベンゾトリアゾール、2−メルカプトベンズイミダ
ゾール、ベンズイミダゾール、2−メルカプトベンゾセ
レナゾール、2−メルカプトベンゾキサゾール、5−メ
ルカプト−3−フェニルチアジアゾール−2−チオン、
2−(o−ヒドロキシフェノール)ベンゾチアゾール、
2,2′−ジチオビス−(ベンゾチアゾール)、フェノ
シアゾリン、ジピリジルアミン、ジピリジル、ジメチル
ヒダントイン、ピロール−2−カルボキシアルデヒド、
2,5−ジメルカプト−1,3,4−チアゾール、5−
アミノ−1,3,4−チアジアゾール−2−チオール、
3−アミノ−1,2,4−トリアゾール、4−アミノ−
1,2,4−トリアゾール、3−アミノ−5−メルカプ
ト−1,2,4−トリアゾール、2−メルカプト−1−
メチルイミダゾール、2−メルカプトチアゾリン、2−
アミノチアゾール、3,5−ジメチルピラゾール、ヒス
チジン、1,10−フェナントロリン、1,8−ジアザ
ビシクロ(5,4,0)ウンデセン−7等、(iii)
直鎖構造の化合物:例えばN−β(アミノエチル)γ
−アミノプロピルトリメトキシシラン、N−β(アミノ
エチル)γ−アミノプロピルメチルジメトキシシラン、
γ−アミノプロピルトリエトキシシラン、N−フェニル
−γ−アミノプロピルトリメトキシシラン、チオカルボ
ヒドラジド、カルボビドラジド、グリシンメチルエステ
ル、アジピックジヒドラジド、アセチダジド、等が挙げ
られ、これらは一種もしくは二種以上の混合物として用
いられる。Specific examples of the organic corrosion inhibitor (b) having a nitrogen atom in the molecule include (i) having a cyclic structure such as a 5-membered ring or a 6-membered ring, and having a nitrogen atom in the cyclic structure; Compounds that do not have: e.g. diphenylthiocarbazone, N,N'-diphenylethylenediamine,
S-diphenylcarbazide, dibenzylamine, 1,5
-Diphenyl-3-thiocarbohydrazide, 1,4-diphenyl-3-thiosemicarbazide, thiocarboanilide, thiobenzanilide, thioacetanilide, etc., (ii) cyclic structures such as 5-membered rings, 6-membered rings, etc. and a nitrogen atom in the cyclic structure: for example, 2-mercaptobenzothiazole, benzotriazole, 1-hydroxy-benzotriazole, 2-mercaptobenzimidazole, benzimidazole, 2-mercaptobenzoselenazole, 2-mercapto Benzoxazole, 5-mercapto-3-phenylthiadiazole-2-thione,
2-(o-hydroxyphenol)benzothiazole,
2,2'-dithiobis-(benzothiazole), phenocyazoline, dipyridylamine, dipyridyl, dimethylhydantoin, pyrrole-2-carboxaldehyde,
2,5-dimercapto-1,3,4-thiazole, 5-
amino-1,3,4-thiadiazole-2-thiol,
3-amino-1,2,4-triazole, 4-amino-
1,2,4-triazole, 3-amino-5-mercapto-1,2,4-triazole, 2-mercapto-1-
Methylimidazole, 2-mercaptothiazoline, 2-
Aminothiazole, 3,5-dimethylpyrazole, histidine, 1,10-phenanthroline, 1,8-diazabicyclo(5,4,0)undecene-7, etc., (iii)
Compounds with a linear structure: e.g. N-β (aminoethyl)γ
-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldimethoxysilane,
Examples include γ-aminopropyltriethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, thiocarbohydrazide, carbohydrazide, glycine methyl ester, adipic dihydrazide, acetidazide, etc., and these may be used alone or in a mixture of two or more. used as.
【0018】本発明に使用される塗料組成物において、
前記腐食抑制剤は、前記水溶性もしくは水分散性有機樹
脂100重量部に対して、0.01〜10重量部(固形
分換算)の割合で配合することが好ましく、前記範囲よ
り配合量が少ない場合には、前記した耐食性、基材との
密着性、シリカ粒子の固定化等の効果が充分発揮されず
、また、前記範囲より過剰に配合すると、皮膜の親水性
及び塗料の安定性が低下する傾向となる。[0018] In the coating composition used in the present invention,
The corrosion inhibitor is preferably blended at a ratio of 0.01 to 10 parts by weight (in terms of solid content) with respect to 100 parts by weight of the water-soluble or water-dispersible organic resin, and the amount blended is less than the above range. In some cases, the aforementioned effects such as corrosion resistance, adhesion to the substrate, and immobilization of silica particles may not be sufficiently exhibited, and if added in excess of the above range, the hydrophilicity of the film and the stability of the coating will decrease. There is a tendency to
【0019】さらに、本発明塗料組成物に使用される(
c)シリカ粒子は皮膜中に存在することで皮膜を粗面化
するとともに、シリカ粒子表面に存在するシラノール基
(−Si−OH) が水分と水素結合し易い為、皮膜の
親水性に寄与するものである。前記シリカ粒子は、水分
散凝集コロイダルシリカ、及び水分散可能な粉末状ヒュ
ームドシリカが代表的なものとして挙げられる。前者、
即ち水分散凝集コロイダルシリカとしては例えば、一般
に市販されているPT−3020〔日産化学工業(株)
製商品〕があり、また後者、即ち水分散可能な粉末状ヒ
ュームドシリカとしては例えば、アエロジル130、同
200、同300、同380、同RX200、同R20
2、同T805、同R805、同R972、同R974
、同R811、同R812、同OX50、同TT600
、同MOX80、同MOX170、同COX84〔日本
アエロジル(株)製商品名〕等が挙げられ、これらは一
種もしくは二種以上の混合物として使用される。Furthermore, (
c) The presence of silica particles in the film roughens the surface of the film, and the silanol groups (-Si-OH) present on the surface of the silica particles easily form hydrogen bonds with moisture, contributing to the hydrophilicity of the film. It is something. Typical examples of the silica particles include water-dispersed agglomerated colloidal silica and water-dispersible powdered fumed silica. former,
That is, as the water-dispersed agglomerated colloidal silica, for example, commercially available PT-3020 [Nissan Chemical Industries, Ltd.]
Examples of the latter, water-dispersible powdery fumed silica, include Aerosil 130, Aerosil 200, Aerosil 300, Aerosil 380, Aerosil RX200, and Aerosil R20.
2. T805, R805, R972, R974
, R811, R812, OX50, TT600
, MOX80, MOX170, COX84 (trade name, manufactured by Nippon Aerosil Co., Ltd.), and these may be used alone or as a mixture of two or more.
【0020】前記シリカ粒子は、皮膜の粗面化効果を大
ならしめるために、水分散状態での粒径〔コールターカ
ウンター(COULTER社製)により測定した平均粒
径〕が50mμ〜2μの範囲にあるものが最も好ましい
。シリカ粒子の粒径があまり小さいと皮膜を粗面化させ
ることが不充分となり、従って親水性も小さくなる。
また、粒径が2μを越えると、皮膜の成膜性(密着性)
及び組成物の安定性が低下する傾向になる。[0020] In order to increase the roughening effect of the film, the silica particles have a particle size in the water dispersion state (average particle size measured with a Coulter Counter (manufactured by COULTER)) in the range of 50 mμ to 2 μm. Some are most preferred. If the particle size of the silica particles is too small, it will be insufficient to roughen the surface of the film, and the hydrophilicity will also be reduced. In addition, if the particle size exceeds 2μ, the film forming property (adhesion)
and the stability of the composition tends to decrease.
【0021】本発明の塗料組成物において、前記(c)
シリカ粒子は、前記水溶性もしくは水分散性有機樹脂1
00重量部に対して好ましくは5〜150重量部(固形
分換算)、より好ましくは10〜120重量部の範囲で
用いることがよい。前記範囲よりもシリカ粒子の量が少
ないと、皮膜への親水性付与が不充分となり、逆に過剰
に用いると皮膜の成膜性(密着性)および組成物の安定
性が低下する傾向になる。[0021] In the coating composition of the present invention, the above (c)
The silica particles are the water-soluble or water-dispersible organic resin 1.
It is preferably used in an amount of 5 to 150 parts by weight (in terms of solid content), more preferably 10 to 120 parts by weight. If the amount of silica particles is less than the above range, the imparting of hydrophilicity to the film will be insufficient, whereas if it is used in excess, the film formability (adhesion) of the film and the stability of the composition will tend to decrease. .
【0022】更に、本発明の塗料組成物を構成する(d
)潤滑剤粉末は、常温及び塗膜形成後も粉末形状を維持
するものが望ましく、該潤滑剤粉末は、得られる塗膜表
面を粗面化させ、潤滑性をもたせ、すなわち動摩擦係数
の低下をもたらし被覆アルミニウム材の成形加工性、特
にプレス成形加工性を向上させるために配合する。この
ような潤滑剤粉末としては、合成ワックス粉末と固体潤
滑剤粉末が代表的なものとして挙げられる。Furthermore, the coating composition of the present invention comprises (d
) It is desirable that the lubricant powder maintains its powder shape at room temperature and after the coating film is formed. It is blended to improve the formability, especially the press formability, of the coated aluminum material. Typical examples of such lubricant powder include synthetic wax powder and solid lubricant powder.
【0023】合成ワックス粉末としては、合成炭化水素
;脂肪酸エステル;脂肪アミド、置換アミドなどの脂肪
酸窒素誘導体;モンタンワックス誘導体、酸化モンタン
ワックスなどの変性ワックス;ポリエチレンワックスな
どの高分子化合物;塩素化パラフィンなどの塩素化ワッ
クス等が代表的なものとして挙げられる。また固体潤滑
剤粉末としては、黒鉛、二硫化モリブデン、二硫化タン
グステン、窒化ホウ素、フッ化黒鉛などの層状固体潤滑
剤;ポリビニルクロライド、ポリスチレン、ポリメチル
(メタ)アクリレート、ポリアミド、高密度ポリエチレ
ン、ポリプロピレン、ポリテトラフルオロエチレンなど
のプラスチック潤滑剤;脂肪酸のカルシウム、バリウム
、リチウム、亜鉛あるいはアルミニウムなどの金属石け
ん等が代表的なものとして挙げられるが、特に表面滑性
が高いプラスチック潤滑剤、金属石けんが望ましい。
特に親水性の観点から金属石けんが最も好ましい。Synthetic wax powders include synthetic hydrocarbons; fatty acid esters; fatty acid nitrogen derivatives such as fatty amides and substituted amides; modified waxes such as montan wax derivatives and montan oxide wax; polymeric compounds such as polyethylene wax; chlorinated paraffins. Typical examples include chlorinated waxes such as . Solid lubricant powders include layered solid lubricants such as graphite, molybdenum disulfide, tungsten disulfide, boron nitride, and graphite fluoride; polyvinyl chloride, polystyrene, polymethyl (meth)acrylate, polyamide, high-density polyethylene, polypropylene, Typical examples include plastic lubricants such as polytetrafluoroethylene; metal soaps made of fatty acids such as calcium, barium, lithium, zinc, or aluminum; plastic lubricants and metal soaps with particularly high surface lubricity are preferred. . In particular, metal soaps are most preferred from the viewpoint of hydrophilicity.
【0024】このような潤滑剤粉末は、前記水溶性また
は水分散性有機樹脂100重量部に対し、約2〜80重
量部配合するのが、塗膜の潤滑性が発揮され、また塗膜
の物理的、化学的強度も過度であるので望ましい。特に
好ましくは5〜60重量部である。また潤滑剤粉末の粒
径は、平均粒径約0.1〜20μmが適当であり、0.
1μm未満のような小さすぎる場合には、塗膜上に潤滑
剤粒子が露出しにくくなるので潤滑性が低下し、成形加
工性に問題が生じ易く、逆に20μmを越えて大きすぎ
る場合には塗膜の成膜性及び塗料安定性が低下する傾向
になる。なお、潤滑剤粉末の粒径の最も好ましい範囲は
0.5〜12μmのものである。It is recommended that such lubricant powder be blended in an amount of about 2 to 80 parts by weight with respect to 100 parts by weight of the water-soluble or water-dispersible organic resin, in order to exhibit the lubricity of the coating film and to improve the coating film's lubricity. It is desirable because it has excessive physical and chemical strength. Particularly preferably 5 to 60 parts by weight. The particle size of the lubricant powder is suitably an average particle size of about 0.1 to 20 μm, and 0.1 to 20 μm.
If it is too small, such as less than 1 μm, the lubricant particles will be difficult to expose on the coating film, resulting in a decrease in lubricity and problems with moldability.On the other hand, if it is too large, exceeding 20 μm, The film forming properties of the coating and the stability of the coating tend to decrease. Note that the most preferable range of particle size of the lubricant powder is 0.5 to 12 μm.
【0025】また、本発明の塗料組成物に使用される(
e)ノニオン系界面活性剤は、塗料中に配合されること
により、シリカ粒子や潤滑剤粉末の分散性を向上させ、
塗料組成物の安定性を向上させることが出来るとともに
、塗膜の親水性、及び親水持続性向上に効果を発揮する
。一般に、塗料組成物等に添加、使用される界面活性剤
としては、ノニオン系以外に、カチオン系、アニオン系
、両性系が知られているが、本発明において、ノニオン
系以外の界面活性剤を単独使用することは、塗料の安定
性、発泡性、塗布性等の点で使用に適さない。[0025] Also used in the coating composition of the present invention (
e) Nonionic surfactants improve the dispersibility of silica particles and lubricant powder by being blended into paints,
The stability of the coating composition can be improved, and it is also effective in improving the hydrophilicity and sustainability of the coating film. In general, cationic, anionic, and amphoteric surfactants are known in addition to nonionic surfactants to be added and used in coating compositions. When used alone, it is not suitable for use in terms of paint stability, foaming properties, coating properties, etc.
【0026】前記(e)ノニオン系界面活性剤としては
、ポリオキシエチレンノニルフェニルエーテル、ポリオ
キシエチレンオクチルフェニルエーテル等のアルキルア
リルエーテル型;ポリオキシエチレンアルキルエーテル
、ポリオキシエチレンラウリルエーテル、ポリオキシエ
チレンオレイルエーテル、ポリオキシエチレントリデシ
ルエーテル、ポリオキシエチレンセチルエーテル、ポリ
オキシエチレンステアリルエーテル等のアルキルエーテ
ル型;ポリオキシエチレンラウレート、ポリオキシエチ
レンオレエート、ポリオキシエチレンステアレート等の
アルキルエステル型;ポリオキシエチレンラウリルアミ
ン等のアルキルアミン型;ソルビタンラウレート、ソル
ビタンパルミテート、ソルビタンステアレート、ソルビ
タンオレエート、ソルビタン脂肪酸エステル、ポリオキ
シエチレンソルビタンラウレート、ポリオキシエチレン
ソルビタンパルミテート、ポリオキシエチレンソルビタ
ンステアレート、ポリオキシエチレンソルビタンオレエ
ート等のソルビタン誘導体などが代表的なものとして挙
げられる。The nonionic surfactants (e) include alkyl allyl ether types such as polyoxyethylene nonylphenyl ether and polyoxyethylene octylphenyl ether; polyoxyethylene alkyl ether, polyoxyethylene lauryl ether, and polyoxyethylene. Alkyl ether types such as oleyl ether, polyoxyethylene tridecyl ether, polyoxyethylene cetyl ether, and polyoxyethylene stearyl ether; alkyl ester types such as polyoxyethylene laurate, polyoxyethylene oleate, and polyoxyethylene stearate; Alkylamine type such as polyoxyethylene laurylamine; sorbitan laurate, sorbitan palmitate, sorbitan stearate, sorbitan oleate, sorbitan fatty acid ester, polyoxyethylene sorbitan laurate, polyoxyethylene sorbitan palmitate, polyoxyethylene sorbitan stear Typical examples include sorbitan derivatives such as ester and polyoxyethylene sorbitan oleate.
【0027】本発明においては、特に乳化、分散性に優
れたアルキルアリルエーテル型ノニオン系界面活性剤が
好ましく、その中でもHLB値が8〜18のものが好ま
しい。尚、本発明においては、本発明の目的を損うこと
がなければノニオン系界面活性剤以外の界面活性剤を少
量併用することも可能である。前記ノニオン系界面活性
剤は、前記水溶性または水分散性樹脂100重量部に対
して、5〜150重量部の割合で使用することが好まし
く、特には10〜100重量部が好ましい。前記範囲よ
り少ないと、潤滑剤粉末の分散性が低下し、又過剰に配
合されると塗膜の耐食性が低下する傾向になる。In the present invention, alkyl allyl ether type nonionic surfactants having particularly excellent emulsifying and dispersing properties are preferred, and among these, those having an HLB value of 8 to 18 are preferred. In the present invention, it is also possible to use a small amount of surfactants other than nonionic surfactants as long as the purpose of the present invention is not impaired. The nonionic surfactant is preferably used in an amount of 5 to 150 parts by weight, particularly preferably 10 to 100 parts by weight, based on 100 parts by weight of the water-soluble or water-dispersible resin. If the amount is less than the above range, the dispersibility of the lubricant powder will decrease, and if it is added in excess, the corrosion resistance of the coating film will tend to decrease.
【0028】尚、本発明の塗料組成物においては皮膜の
耐食性をより向上せしめるために、(a)水溶性または
水分散性有機樹脂と架橋する水溶性または水分散性アミ
ノ樹脂を、(a)成分有機樹脂100重量部(固形分換
算)に対して、好ましくは50重量部以下、特に5〜4
0重量部程度添加することが好ましい。前記水溶性また
は水分散性アミノ樹脂としては、通常市販されているメ
ラミン樹脂またはベンゾグアナミン樹脂が挙げられ、こ
れらは単独もしくは混合物として使用される。In the coating composition of the present invention, in order to further improve the corrosion resistance of the film, (a) a water-soluble or water-dispersible amino resin crosslinked with a water-soluble or water-dispersible organic resin; Preferably 50 parts by weight or less, especially 5 to 4 parts by weight, based on 100 parts by weight (solid content) of the component organic resin.
It is preferable to add about 0 parts by weight. Examples of the water-soluble or water-dispersible amino resin include commercially available melamine resins and benzoguanamine resins, which may be used alone or as a mixture.
【0029】本発明の塗料組成物には、前記以外の成分
、例えば水溶性フェノール樹脂;有機溶材;水溶性フェ
ノール樹脂やブロック化イソシアネート樹脂等の架橋剤
;有機又は無機顔料;分散剤;沈殿防止剤;レベリング
剤;消泡剤等通常塗料組成物に併用されている各種成分
を必要により添加してもよい。本発明の塗料組成物は、
前記各成分と水を固形分が2〜30重量%になるように
混合して製造することができる。The coating composition of the present invention may contain components other than those mentioned above, such as water-soluble phenolic resin; organic solvent; crosslinking agent such as water-soluble phenolic resin or blocked isocyanate resin; organic or inorganic pigment; dispersing agent; Various components commonly used in coating compositions, such as agents; leveling agents; antifoaming agents, etc., may be added as necessary. The coating composition of the present invention is
It can be manufactured by mixing each of the above components and water so that the solid content is 2 to 30% by weight.
【0030】得られた塗料組成物は、例えばアルミニウ
ム、その他の金属等の表面上にスプレー、ロールコート
、シャワーコート等の塗装手段により塗装され、60〜
300℃、好ましくは100〜250℃程度の温度で乾
燥または硬化させる。尚、特にアルミニウムの場合には
、その用途を考慮して乾燥膜厚0.1〜10μm、好ま
しくは0.1〜5μm程度の皮膜とすることが必要であ
る。The obtained coating composition is applied onto the surface of aluminum, other metals, etc. by a coating method such as spraying, roll coating, or shower coating.
Drying or curing is carried out at a temperature of about 300°C, preferably about 100 to 250°C. In particular, in the case of aluminum, it is necessary to take into account its use and to form a film with a dry film thickness of about 0.1 to 10 μm, preferably about 0.1 to 5 μm.
【0031】[0031]
【発明の効果】本発明の塗料組成物は、塗料の安定性に
優れているとともに、耐食性や親水性及びプレス加工性
に優れた皮膜を提供でき、従って特にアルミニウム表面
等に塗布して例えばフィン材等に使用すると優れた効果
を発揮するものである。従来、シリカ粒子に代えられる
ような粒径50mμ〜20μm程度の無機微粒子、例え
ば炭酸カルシウム、水酸化鉄等が知られているが、シリ
カ粒子ほど多孔質ではなく、従って比表面積もシリカ粒
子に比べて小さいため、皮膜の粗面化に充分寄与出来ず
、又シラノール基の如き水と親和し易い基が存在しない
ため、親水性付与効果は期待できないものである。Effects of the Invention The coating composition of the present invention has excellent coating stability and can provide a film with excellent corrosion resistance, hydrophilicity, and press workability. It exhibits excellent effects when used for materials, etc. Conventionally, inorganic fine particles with a particle size of about 50 to 20 μm, such as calcium carbonate and iron hydroxide, have been known to replace silica particles, but they are not as porous as silica particles, and therefore have a specific surface area compared to silica particles. Because of their small size, they cannot sufficiently contribute to roughening the surface of the film, and because there are no groups such as silanol groups that are easily compatible with water, no effect on imparting hydrophilicity can be expected.
【0032】本発明においては、(c)シリカ粒子の効
果は勿論のこと、(a)水溶性もしくは水分散性有機樹
脂と(b)分子中に窒素原子を有する有機腐食抑制剤、
(d)潤滑剤粉末及び(e)ノニオン系界面活性剤とを
組合わせることによって所期目的の効果が得られるので
ある。In the present invention, in addition to the effects of (c) silica particles, (a) a water-soluble or water-dispersible organic resin and (b) an organic corrosion inhibitor having a nitrogen atom in its molecule,
The desired effect can be obtained by combining (d) lubricant powder and (e) nonionic surfactant.
【0033】[0033]
【実施例】以下、本発明を製造例、実施例及び比較例に
よりさらに詳しく説明する。「部」及び「%」は、各々
「重量部」及び「重量%」を示す。
製造例1
撹拌機を付けた2リットルの三ツ口フラスコにイソプロ
ピルアルコール1000gを入れ、70℃に加温する。
アゾビスイソブチロニトリル5gを添加した後、アクリ
ル酸25g、2−ヒドロキシエチルメタクリレート40
0g、メチルメタクリレート50g、スチレン25gを
混合したモノマー混合物を3時間かけて滴下し、更に3
時間重合を続けて、アクリル樹脂溶液を得た。これにア
ンモニアをpH=7.5になるように添加し、更に10
00gの水を徐々に滴下して、加熱残分19重量%、樹
脂固形分あたり水酸基価345mg KOH/g、酸価
39mg KOH/gの水溶性アクリル樹脂組成物(A
)を得た。
製造例2
撹拌機を付けた2リットルの三ツ口フラスコにイソプロ
ピルアルコール1000gを入れ、70℃に加温する。
アゾビスイソブチロニトリル5gを添加した後、アクリ
ル酸100g、2−ヒドロキシエチルメタクリレート2
50g、メチルメタクリレート100g、スチレン50
gを混合したモノマー混合物を3時間かけて滴下し、更
に3時間重合を続けて、アクリル樹脂溶液を得た。これ
にトリエチルアミンをpH=7.5になるように添加し
、更に1000gの水を徐々に滴下して、加熱残分19
重量%、樹脂固形分あたり水酸基価216mg KOH
/g、酸価156mg KOH/gの水溶性アクリル樹
脂組成物(B)を得た。
製造例3
撹拌機を付けた2リットルの三ツ口フラスコにイソプロ
ピルアルコール1000gを入れ、70℃に加温する。
アゾビスイソブチロニトリル5gを添加した後、アクリ
ル酸170g、2−ヒドロキシエチルメタクリレート7
5g、メチルメタクリレート200g、スチレン50g
を混合したモノマー混合物を3時間かけて滴下し、更に
3時間重合を続けて、アクリル樹脂溶液を得た。これに
アンモニアをpH=7.5になるように添加し、更に1
000gの水を徐々に滴下して、加熱残分19重量%、
樹脂固形分あたり水酸基価65mg KOH/g、酸価
273mg KOH/gの水溶性アクリル樹脂組成物(
C)を得た。
製造例4(比較)
撹拌機を付けた2リットルの三ツ口フラスコに、水50
0g、イソプロピルアルコール500gを入れ、80℃
に加温する。過硫酸カリウム10gを添加した後、アク
リル酸5g、2−ヒドロキシエチルメタクリレート20
g、メタクリル酸ジメチルアミノエチルメチルクロライ
ド塩150g、メチルメタクリレート225g、スチレ
ン100gを混合したモノマーを3時間かけて滴下し、
更に4時間重合を続けて、アクリル樹脂溶液を得た。こ
れにアンモニアをpH=7.5になるように添加し、更
に水1000gの水を徐々に滴下して、加熱残分20重
量%、樹脂固形分あたり水酸基価17mg KOH/g
、酸価8mgKOH/gの水溶性アクリル樹脂組成物(
D)を得た。
製造例5(比較)
撹拌機を付けた2リットルの三ツ口フラスコに、イソプ
ロピルアルコール1000gを入れ、70℃に加温する
。アゾビスイソブチロニトリル5gを添加した後、アク
リル酸300g、メチルメタクリレート125g、スチ
レン75gを混合したモノマー混合物を3時間かけて滴
下し、更に3時間重合を続けて、アクリル樹脂溶液を得
た。これにアンモニアをpH=7.5になるように添加
し、更に1000gの水を徐々に滴下して、加熱残分1
8重量%、樹脂固形分あたり水酸基価0mg KOH/
g、酸価468mg KOH/gの水溶性アクリル樹脂
組成物(E)を得た。
実施例1
水溶性アクリル樹脂組成物(A)526部、および3−
アミノ−5−メルカプト−1,2,4−トリアゾール0
.05部、および水分散凝集コロイダルシリカ〔PT−
3020:日産化学工業(株)製商品名:固形分20%
、粒径0.2μm〕300部、水溶性アミノ樹脂〔スミ
マールMC−1:住友化学工業(株)製商品名:固形分
75%〕13部、界面活性剤〔ニューコール564:日
本乳化剤(株)製商品名:固形分100%〕10部、ス
テアリン酸アルミニウム〔SA−2000:堺化学工業
(株)製商品名、平均粒径6μm〕20部を混合し、水
にて固形分が18%になるよう塗料を調整した。得られ
た塗料を脱脂、洗浄した板厚0.12mmの工業用純ア
ルミニウム(JIS A 1100) に乾燥膜厚が2
μmとなるようロールコート塗装し、200℃で30秒
焼付けて、密着性、耐食性、親水性、親水持続性、動摩
擦係数、更に塗料安定性試験を行ない、その結果を表2
に示した。
実施例2〜7及び比較例1〜5
下記表1に示した配合割合で各成分を混合し、次いで水
を加えて固形分が8%になるよう調整し、各塗料組成物
を得た後、前記実施例1と同様にして比較試験を行ない
、その結果を表2に示した。EXAMPLES The present invention will be explained in more detail below with reference to production examples, working examples, and comparative examples. "Parts" and "%" indicate "parts by weight" and "% by weight," respectively. Production Example 1 1000 g of isopropyl alcohol is placed in a 2 liter three-necked flask equipped with a stirrer and heated to 70°C. After adding 5 g of azobisisobutyronitrile, 25 g of acrylic acid, 40 g of 2-hydroxyethyl methacrylate
A monomer mixture of 0 g, 50 g of methyl methacrylate, and 25 g of styrene was added dropwise over 3 hours, and then
Polymerization was continued for hours to obtain an acrylic resin solution. Add ammonia to this so that the pH = 7.5, and then add 10
00 g of water was gradually added dropwise to prepare a water-soluble acrylic resin composition (A
) was obtained. Production Example 2 1000 g of isopropyl alcohol is placed in a 2 liter three-necked flask equipped with a stirrer and heated to 70°C. After adding 5 g of azobisisobutyronitrile, 100 g of acrylic acid, 2-hydroxyethyl methacrylate
50g, methyl methacrylate 100g, styrene 50
A monomer mixture containing g was added dropwise over 3 hours, and polymerization was continued for an additional 3 hours to obtain an acrylic resin solution. Triethylamine was added to this so that the pH was 7.5, and then 1000 g of water was gradually added dropwise, leaving a heating residue of 19.
Weight%, hydroxyl value per resin solid content 216mg KOH
A water-soluble acrylic resin composition (B) having an acid value of 156 mg KOH/g and an acid value of 156 mg KOH/g was obtained. Production Example 3 1000 g of isopropyl alcohol is placed in a 2 liter three-necked flask equipped with a stirrer and heated to 70°C. After adding 5 g of azobisisobutyronitrile, 170 g of acrylic acid, 7 g of 2-hydroxyethyl methacrylate
5g, methyl methacrylate 200g, styrene 50g
A monomer mixture containing the above was added dropwise over 3 hours, and polymerization was continued for an additional 3 hours to obtain an acrylic resin solution. Add ammonia to this so that the pH = 7.5, and then add 1
000g of water was gradually added dropwise until the heating residue was 19% by weight.
Water-soluble acrylic resin composition with a hydroxyl value of 65 mg KOH/g and an acid value of 273 mg KOH/g per resin solid content (
C) was obtained. Production example 4 (comparison) In a 2 liter three-necked flask equipped with a stirrer, add 50 ml of water.
Add 0g and 500g of isopropyl alcohol and heat to 80°C.
Warm to. After adding 10 g of potassium persulfate, 5 g of acrylic acid, 20 g of 2-hydroxyethyl methacrylate
g, 150 g of dimethylaminoethyl methacrylate methyl chloride salt, 225 g of methyl methacrylate, and 100 g of styrene were added dropwise over 3 hours.
Polymerization was continued for an additional 4 hours to obtain an acrylic resin solution. Ammonia was added to this so that the pH was 7.5, and 1000 g of water was gradually added dropwise to give a heating residue of 20% by weight and a hydroxyl value of 17 mg KOH/g per resin solid content.
, a water-soluble acrylic resin composition with an acid value of 8 mgKOH/g (
D) was obtained. Production Example 5 (Comparative) 1000 g of isopropyl alcohol is placed in a 2 liter three-necked flask equipped with a stirrer and heated to 70°C. After adding 5 g of azobisisobutyronitrile, a monomer mixture of 300 g of acrylic acid, 125 g of methyl methacrylate, and 75 g of styrene was added dropwise over 3 hours, and polymerization was continued for an additional 3 hours to obtain an acrylic resin solution. Ammonia was added to this so that the pH was 7.5, and then 1000 g of water was gradually added dropwise, leaving 1 of the heated residue.
8% by weight, hydroxyl value 0mg per resin solid content KOH/
A water-soluble acrylic resin composition (E) having an acid value of 468 mg KOH/g and an acid value of 468 mg KOH/g was obtained. Example 1 526 parts of water-soluble acrylic resin composition (A), and 3-
Amino-5-mercapto-1,2,4-triazole 0
.. 05 parts, and water-dispersed agglomerated colloidal silica [PT-
3020: Manufactured by Nissan Chemical Industries, Ltd. Product name: Solid content 20%
, particle size 0.2 μm] 300 parts, water-soluble amino resin [Sumimar MC-1: trade name manufactured by Sumitomo Chemical Co., Ltd.: solid content 75%] 13 parts, surfactant [Nukol 564: Nippon Nyukazai Co., Ltd. ) product name: solid content 100%] and 20 parts of aluminum stearate [SA-2000: Sakai Chemical Industry Co., Ltd. product name, average particle size 6 μm] were mixed, and with water the solid content was 18%. I adjusted the paint to make it look like this. The resulting paint was degreased and washed to a dry film thickness of 2 on industrial pure aluminum (JIS A 1100) with a thickness of 0.12 mm.
µm, baked at 200℃ for 30 seconds, and tested for adhesion, corrosion resistance, hydrophilicity, hydrophilicity persistence, dynamic friction coefficient, and paint stability.The results are shown in Table 2.
It was shown to. Examples 2 to 7 and Comparative Examples 1 to 5 Each component was mixed in the proportions shown in Table 1 below, and then water was added to adjust the solid content to 8% to obtain each coating composition. A comparative test was conducted in the same manner as in Example 1, and the results are shown in Table 2.
【0034】[0034]
【表1】[Table 1]
【0035】
有機樹脂 (A):水溶性アクリル樹脂組成物(A)
(B):水溶性アクリル樹脂組成物(B)(C):水溶
性アクリル樹脂組成物(C)(D):水溶性アクリル樹
脂組成物(D)(E):水溶性アクリル樹脂組成物(E
)腐食抑制剤(1):3−アミノ−5−メルカプト−1
,2,4−トリアゾール
(2):ベンズイミダゾール
(3):ジピリジルアミン
(4):カテコール
無機粒子 (1):凝集コロイダルシリカ〔PT−3
020:日産化学工業(株)製商品名:水分散タイプ固
形分20%:粒径0.2μm〕
(2):ヒュームドシリカ〔アエロジル200:日本ア
エロジル(株)製商品名〕
(3):炭酸カルシウム〔PS−5:米庄石灰工業(株
)製商品:水分散タイプ固形分70%:粒径0.5μm
〕
潤滑剤粉末(1):ステアリン酸アルミニウム〔SA−
2000:堺化学工業(株)製商品名:平均粒径6μm
〕
(2):ステアリン酸亜鉛〔SZ−2000:堺化学工
業(株)製商品名:平均粒径5μm〕
(3):ステアリン酸カルシウム〔SC−100:堺化
学工業(株)製商品名:平均粒径3μm〕界面活性剤(
1):ニューコール564〔日本乳化剤(株)製商品名
:固形分100%:ノニオン系〕(2):ニューコール
860〔日本乳化剤(株)製商品名:固形分100%:
ノニオン系〕
(3):テクノールIL〔日本乳化剤(株)製商品名:
固形分100%:カチオン系〕
(4):ニューコール290M〔日本乳化剤(株)製商
品名:固形分75%:アニオン系〕
アミノ樹脂(1):スミマールMC−1〔住友化学工業
(株)製商品名:固形分75%〕Organic resin (A): Water-soluble acrylic resin composition (A)
(B): Water-soluble acrylic resin composition (B) (C): Water-soluble acrylic resin composition (C) (D): Water-soluble acrylic resin composition (D) (E): Water-soluble acrylic resin composition ( E
) Corrosion inhibitor (1): 3-amino-5-mercapto-1
, 2,4-triazole (2): benzimidazole (3): dipyridylamine (4): catechol inorganic particles (1): aggregated colloidal silica [PT-3
020: Product name manufactured by Nissan Chemical Industries, Ltd.: Water dispersion type Solid content 20%: Particle size 0.2 μm] (2): Fumed silica [Aerosil 200: Product name manufactured by Nippon Aerosil Co., Ltd.] (3): Calcium carbonate [PS-5: Product manufactured by Yonesho Lime Industry Co., Ltd.: Water dispersion type Solid content 70%: Particle size 0.5 μm
] Lubricant powder (1): Aluminum stearate [SA-
2000: Manufactured by Sakai Chemical Industry Co., Ltd. Product name: Average particle size 6 μm
] (2): Zinc stearate [SZ-2000: Sakai Chemical Industry Co., Ltd. product name: average particle size 5 μm] (3): Calcium stearate [SC-100: Sakai Chemical Industry Co., Ltd. product name: Average Particle size: 3 μm] Surfactant (
1): Nucol 564 [Product name manufactured by Nippon Nyukazai Co., Ltd.: Solid content 100%: Nonionic] (2): Nucoal 860 [Product name manufactured by Nippon Nyukazai Co., Ltd.: Solid content 100%:
Nonionic] (3): Technol IL [Product name manufactured by Nippon Nyukazai Co., Ltd.:
Solid content 100%: cationic] (4): Nucor 290M [Product name manufactured by Nippon Nyukazai Co., Ltd.: Solid content 75%: anionic] Amino resin (1): Sumimaru MC-1 [Sumitomo Chemical Co., Ltd.] Product name: Solid content 75%]
【0036】[0036]
【表2】[Table 2]
【0037】試験方法
■ 密着性─縦横各11本の2mm間隔の直交する切
れ目をナイフで素材に到達するまで入れて、格子状に一
辺の長さ2mmの正方形を100個作った後、セロハン
粘着テープを貼り付け、瞬時にはがした時、はがれずに
残った正方形の数で判定した。Test method ■ Adhesion - After making 100 squares with a side length of 2 mm in a grid pattern by making 11 perpendicular cuts at 2 mm intervals in the vertical and horizontal directions until they reach the material, the cellophane adhesive was When the tape was applied and instantly removed, the number of squares that remained without peeling was judged.
【0038】○─100/100, △─90/10
0〜99/100,×─89/100以下■ 耐食性
─35℃、5重量%NaClを4時間噴霧→60℃にて
2時間乾燥→50℃、95%RH(湿潤)中に2時間放
置を1サイクルとして、サイクル腐食試験を行ない、1
00サイクル後の白さび発生状況で評価した。0038]○─100/100, △─90/10
0 to 99/100, x - 89/100 or less ■ Corrosion resistance - Sprayed with 5 wt% NaCl at 35℃ for 4 hours → Dry at 60℃ for 2 hours → Leave in 50℃, 95% RH (humidity) for 2 hours As one cycle, a cycle corrosion test is carried out,
Evaluation was made based on the appearance of white rust after 00 cycles.
【0039】
◎─白さび5%未満(面積比)
○─白さび15%未満(面積比)
×─白さび15%超(面積比)
■ 親水性 ─ 水道水の入ったビーカ
ーに試験板を浸漬し、引き上げ、水(水濡れ性)
平に試験板を置いた時の塗板表面の水の濡れの状態を
目視で判定する○─全面に水が濡れ水玉の発生がない状
態×─水がはじいて水玉が発生し、濡れない部分が発生
した状態
■ 親水持続性 ─ トリクロロエタン(クロロ
センSM:ダウケミカル社製)の蒸気で5分間脱脂処理
を施した試験板を水道水中に350時間浸漬したのち、
80℃で5分間乾燥させ、上記の親水性試験により判定
する。
■ 動摩擦係数(潤滑性)─表面性測定機HEIDO
N−14(新東科学社製)を用いて、荷重200g、ボ
ール圧子φ10mm、移動速度50mm/分の条件にて
測定した。◎─White rust less than 5% (area ratio) ○─White rust less than 15% (area ratio) ×─White rust more than 15% (area ratio) ■ Hydrophilicity - Place the test plate in a beaker containing tap water Soak, pull out, water (water wettability)
Visually judge the state of water wetting on the surface of the coated plate when the test plate is placed flat. ○ - Water is wet on the entire surface and there are no droplets. Conditions that occur ■ Hydrophilicity - After a test plate that has been degreased with trichloroethane (Chlorocene SM: manufactured by Dow Chemical Company) for 5 minutes in tap water for 350 hours,
It is dried at 80° C. for 5 minutes and judged by the hydrophilicity test described above. ■ Coefficient of dynamic friction (lubricity) - Surface quality measuring device HEIDO
Measurement was performed using N-14 (manufactured by Shinto Kagakusha) under the conditions of a load of 200 g, a ball indenter of φ10 mm, and a moving speed of 50 mm/min.
【0040】
◎─動摩擦係数0.25未満
○─動摩擦係数0.25〜0.35未満×─動摩擦係数
0.35以上
■ 塗料安定性─ 50℃の恒温槽中に塗料の
入ったサンプル管を静置し、2週間後の塗料の状態を判
定する。◎─Dynamic friction coefficient less than 0.25○─Dynamic friction coefficient 0.25 to less than 0.35×─Dynamic friction coefficient 0.35 or more ■Paint stability─ A sample tube containing the paint in a constant temperature bath at 50°C Let stand and judge the condition of the paint after 2 weeks.
【0041】
○─初期の状態とほとんど変化なし
×─増粘または、ゲル状になる
前記比較試験結果より明らかに、本発明塗料組成物から
得られた皮膜は、耐食性、密着性、親水性に優れるとと
もに、塗料安定性も非常に良好であった。一方、シリカ
粒子を配合しない系(比較例1)、潤滑剤粉末を配合し
ない系(比較例2)、界面活性剤を配合しない系(比較
例3)、カチオン系界面活性剤を用いた系(比較例4)
、及び腐食抑制剤を配合しない系はいずれも、本発明よ
り各性能が劣るものであった。○ - Almost no change from the initial state × - Thickening or becoming gel-like It is clear from the above comparative test results that the film obtained from the coating composition of the present invention has excellent corrosion resistance, adhesion, and hydrophilicity. In addition to being excellent, the coating stability was also very good. On the other hand, a system containing no silica particles (Comparative Example 1), a system containing no lubricant powder (Comparative Example 2), a system containing no surfactant (Comparative Example 3), and a system containing a cationic surfactant (Comparative Example 3) Comparative example 4)
, and the system without a corrosion inhibitor were all inferior in performance to the present invention.
Claims (2)
(b)分子中に窒素原子を有する有機腐食抑制剤、(c
)シリカ粒子、(d)潤滑剤粉末、(e)ノニオン系界
面活性剤、及び(f)水 から成る塗料組成物。Claim 1: (a) a water-soluble or water-dispersible organic resin;
(b) an organic corrosion inhibitor having a nitrogen atom in the molecule, (c
A coating composition comprising:) silica particles, (d) lubricant powder, (e) nonionic surfactant, and (f) water.
(b)分子中に窒素原子を有する有機腐食抑制剤、(c
)シリカ粒子、(d)潤滑剤粉末、及び(e)ノニオン
系界面活性剤 から成る親水性皮膜を有する被覆アルミニウム材。Claim 2: (a) a water-soluble or water-dispersible organic resin;
(b) an organic corrosion inhibitor having a nitrogen atom in the molecule, (c
) A coated aluminum material having a hydrophilic film consisting of silica particles, (d) lubricant powder, and (e) nonionic surfactant.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8513691A JPH04318071A (en) | 1991-04-17 | 1991-04-17 | Coating compound composition and coated aluminum material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP8513691A JPH04318071A (en) | 1991-04-17 | 1991-04-17 | Coating compound composition and coated aluminum material |
Publications (1)
Publication Number | Publication Date |
---|---|
JPH04318071A true JPH04318071A (en) | 1992-11-09 |
Family
ID=13850240
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP8513691A Pending JPH04318071A (en) | 1991-04-17 | 1991-04-17 | Coating compound composition and coated aluminum material |
Country Status (1)
Country | Link |
---|---|
JP (1) | JPH04318071A (en) |
Cited By (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0734030A (en) * | 1993-07-20 | 1995-02-03 | Dainippon Toryo Co Ltd | Coating composition and coated aluminum material |
JPH07196977A (en) * | 1993-12-28 | 1995-08-01 | Dainippon Toryo Co Ltd | Coating composition and coated aluminum material |
EP0878519A1 (en) * | 1997-05-14 | 1998-11-18 | Nippon Paint Co., Ltd. | Anticorrosive coating composition and anticorrosion treatment method |
JP2012236900A (en) * | 2011-05-11 | 2012-12-06 | Stt Kk | Water-based lubricating coating composition |
WO2017159706A1 (en) * | 2016-03-17 | 2017-09-21 | ダイセルポリマー株式会社 | Pas resin composition |
WO2022176724A1 (en) * | 2021-02-16 | 2022-08-25 | ソマール株式会社 | Liquid composition, membrane, and product comprising membrane |
-
1991
- 1991-04-17 JP JP8513691A patent/JPH04318071A/en active Pending
Cited By (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH0734030A (en) * | 1993-07-20 | 1995-02-03 | Dainippon Toryo Co Ltd | Coating composition and coated aluminum material |
JPH07196977A (en) * | 1993-12-28 | 1995-08-01 | Dainippon Toryo Co Ltd | Coating composition and coated aluminum material |
EP0878519A1 (en) * | 1997-05-14 | 1998-11-18 | Nippon Paint Co., Ltd. | Anticorrosive coating composition and anticorrosion treatment method |
US5969019A (en) * | 1997-05-14 | 1999-10-19 | Nippon Paint Co., Ltd. | Anticorrosive coating composition and anticorrosion treatment method |
JP2012236900A (en) * | 2011-05-11 | 2012-12-06 | Stt Kk | Water-based lubricating coating composition |
WO2017159706A1 (en) * | 2016-03-17 | 2017-09-21 | ダイセルポリマー株式会社 | Pas resin composition |
JPWO2017159706A1 (en) * | 2016-03-17 | 2019-01-24 | ダイセルポリマー株式会社 | PAS resin composition |
WO2022176724A1 (en) * | 2021-02-16 | 2022-08-25 | ソマール株式会社 | Liquid composition, membrane, and product comprising membrane |
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A02 | Decision of refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A02 Effective date: 20000214 |